Senescence- and death-related alteration of chlorophylls and carotenoids in marine phytoplankton

Abstract This report extends previous work ( Louda et al., 1998a , Louda et al., 1998b . Chlorophyll degradation during senescence and death. Organic Geochemistry 29, 1233–1251.) in which we detailed type-I (alteration) and -II (destruction) degradation of chlorophyll with representative fresh water phytoplankton. The present study covers similar experiments with marine phytoplankton, namely, a cyanobacterium (“ANA” Anacystis sp), a coccolithophore (“COC” Coccolithophora sp.), a dinoflagellate (“GYM” Gymnodinium sp.) and two diatoms (“CYC” Cyclotella meneghiniana and “THAL” Thalassiosira sp.). Mg loss (‘pheophytinization') was rapid and continuous in all species under room-oxic conditions and slow or sporadic under anoxic conditions. The proportion of dephytylated pigments (pheophorbides-a, chlorophyllides-a), relative to the phytylated forms (chlorophyll-a, pheophytins-a), increased over the first year under room-oxic conditions and in room-anoxic conditions only in “CYC”. Pheophorbide-a was converted to pyropheophorbide-a within 15 months only in “THAL” and “ANA”, and slightly in “COC”. After 9–15 months of oxic incubation, “COC” was found to contain traces of purpurin-18 phytyl ester. Consideration of carotenoid pigments is also included herein. All fucoxanthin containing species, except “THAL”, exhibited conversion of fucoxanthin to fucoxanthinol in room-oxic conditions. Diadinoxanthin was rapidly de-epoxidized to give diatoxanthin within the first 2–4 weeks. Diatoxanthin then disappeared from all species by 15 months with a concurrent increase in a pigment which we tentatively identify as a cis-zeaxanthin. Incubations of pure cultures are found to be an effective way by which to model the early type-I reactions for both chlorophylls and carotenoids. The influence of oxygen during senescence-death and the onset of early diagenesis is of paramount importance. The absence of oxygen and, by inference, aerobic microbiota, retards the breakdown of these pigments dramatically.

[1]  Strand,et al.  Geometrical E/Z isomers of (6R)- and (6S)-neoxanthin and biological implications. , 2000, Biochemical systematics and ecology.

[2]  James R. Nelson Rates and possible mechanism of light-dependent degradation of pigments in detritus derived from phytoplankton , 1993 .

[3]  M. Sohn Organic marine geochemistry , 1986 .

[4]  田中 淑人,et al.  海綿動物Tethya amamensisからえられた二種の7-シスアロマティクカロテノイド , 1982 .

[5]  R. Ocampo,et al.  Structural comparison of nickel, vanadyl, copper, and free base porphyrins from Oulad Abdoun oil shale (Maastrichtian, Morocco) , 1990 .

[6]  A. Treibs Chlorophyll‐ und Häminderivate in organischen Mineralstoffen , 1936 .

[7]  R. Ocampo,et al.  Structural determination of purpurin-18 (as methyl ester) from sedimentary organic matter , 1999 .

[8]  S. W. Jeffrey Algal Pigment Systems , 1980 .

[9]  Crystal S. Thomas,et al.  Computer-assisted high-performance liquid chromatography method development with applications to the isolation and analysis of phytoplankton pigments. , 2001, Journal of chromatography. A.

[10]  N. Spooner,et al.  Biologically mediated defunctionalization of chlorophyll in the aquatic environment - I. Senescence/decay of the diatom Phaeodactylum tricornutum , 1994 .

[11]  E. W. Baker,et al.  Early diagenetic alteration of chlorophyll-a and bacteriochlorophyll-a in a contemporaneous marl ecosystem; Florida Bay , 2000 .

[12]  J. Katz,et al.  Preparation and properties of 10-hydroxychlorophylls a and b. , 1967, Journal of the American Chemical Society.

[13]  S. Jeffrey,et al.  Chlorophyllase distribution in ten classes of phytoplankton: a problem for chlorophyll analysis , 1987 .

[14]  J. Maxwell,et al.  NMR studies of sedimentary tetrapyrroles , 1990 .

[15]  S. Carpenter,et al.  Chlorophyll production, degradation, and sedimentation: Implications for paleolimnology1 , 1986 .

[16]  B. Keely,et al.  Sedimentary purpurins: oxidative transformation products of chlorophylls , 1998 .

[17]  J. Katz,et al.  Chlorophyll diastereoisomers. Nature of chlorophylls a' and b' and evidence for bacteriochlorophyll epimers from proton magnetic resonance studies , 1968 .

[18]  R. Parkes,et al.  FORMATION OF MESOPYROPHAEOPHORBIDE A DURING ANAEROBIC BACTERIAL-DEGRADATION OF THE MARINE PRYMNESIOPHYTE EMILIANIA- HUXLEYI , 1995 .

[19]  E. W. Baker,et al.  The biogeochemistry of chlorophyll , 1986 .

[20]  E. Head,et al.  Chlorophyll and carotenoid transformation and destruction by Calanus spp. grazing on diatoms , 1992 .

[21]  P. Falkowski Primary productivity in the sea , 1980 .

[22]  J. Hurley,et al.  Fluxes and transformations of aquatic pigments in Lake Mendota, Wisconsin , 1990 .

[23]  R. Johns,et al.  Biological markers in the sedimentary record , 1988 .

[24]  E. W. Baker,et al.  Chlorophyll-a degradation during cellular senescence and death , 1998 .

[25]  H. Thomas,et al.  Chlorophyll Breakdown in Senescent Leaves , 1996, Plant physiology.

[26]  S. Wright,et al.  Phytoplankton Pigments in Oceanography: Guidelines to Modern Methods , 1997 .

[27]  C. Boreham,et al.  Origin of petroporphyrins. 2. Evidence from stable carbon isotopes. , 1990, Energy & fuels : an American Chemical Society journal.

[28]  A. Treibs Über das Vorkommen von Chlorophyllderivaten in einem Ölschiefer aus der oberen Trias , 1934 .

[29]  S. W. Jeffrey,et al.  Data for the identification of 47 key phytoplankton pigments , 1997 .

[30]  R. Gagosian,et al.  Carotenoid transformations in coastal marine waters , 1982, Nature.

[31]  E. Furlong,et al.  Pigment preservation and remineralization in oxic coastal marine sediments , 1988 .

[32]  C. Llewellyn,et al.  The rapid determination of algal chlorophyll and carotenoid pigments and their breakdown products in natural waters by reverse-phase high-performance liquid chromatography , 1983 .

[33]  J. Conant,et al.  STUDIES IN THE CHLOROPHYLL SERIES. IV. THE DEGRADATION OF CHLOROPHYLL AND ALLOMERIZED CHLOROPHYLL TO SIMPLE CHLORINS , 1931 .

[34]  Stanley B. Brown,et al.  THE DEGRADATION OF CHLOROPHYLL - A BIOLOGICAL ENIGMA. , 1987, The New phytologist.